WO2020073040A1 - Matériaux de support pour impression tridimensionnelle - Google Patents

Matériaux de support pour impression tridimensionnelle

Info

Publication number
WO2020073040A1
WO2020073040A1 PCT/US2019/054961 US2019054961W WO2020073040A1 WO 2020073040 A1 WO2020073040 A1 WO 2020073040A1 US 2019054961 W US2019054961 W US 2019054961W WO 2020073040 A1 WO2020073040 A1 WO 2020073040A1
Authority
WO
WIPO (PCT)
Prior art keywords
support material
cellulose
vinyl pyrrolidone
vinyl
copolymers
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/US2019/054961
Other languages
English (en)
Inventor
Zhendong Liu
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Hercules LLC
Original Assignee
Hercules LLC
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Hercules LLC filed Critical Hercules LLC
Priority to US17/282,949 priority Critical patent/US20210387422A1/en
Publication of WO2020073040A1 publication Critical patent/WO2020073040A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y70/00—Materials specially adapted for additive manufacturing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
    • B29C64/40—Structures for supporting 3D objects during manufacture and intended to be sacrificed after completion thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y10/00—Processes of additive manufacturing
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
    • C08L1/08—Cellulose derivatives
    • C08L1/26—Cellulose ethers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
    • C08L1/08—Cellulose derivatives
    • C08L1/26—Cellulose ethers
    • C08L1/28—Alkyl ethers
    • C08L1/284—Alkyl ethers with hydroxylated hydrocarbon radicals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L39/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Compositions of derivatives of such polymers
    • C08L39/04—Homopolymers or copolymers of monomers containing heterocyclic rings having nitrogen as ring member
    • C08L39/06—Homopolymers or copolymers of N-vinyl-pyrrolidones
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2001/00—Use of cellulose, modified cellulose or cellulose derivatives, e.g. viscose, as moulding material
    • B29K2001/08—Cellulose derivatives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y70/00—Materials specially adapted for additive manufacturing
    • B33Y70/10—Composites of different types of material, e.g. mixtures of ceramics and polymers or mixtures of metals and biomaterials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y80/00—Products made by additive manufacturing

Definitions

  • the presently disclosed process(es), procedure ⁇ ), method(s), product(s), result(s), and/or concept(s) (collectively referred to hereinafter as the“present disclosure”) relates generally to a support material for three-dimensional printing comprising a blend of at least two cellulose ethers or a blend of at least one cellulose ether and at least one vinyl pyrrolidone polymer. Additionally, the present disclosure relates to a shaped material and a three- dimensionally printed object comprising the support material. Furthermore, a process for producing a three-dimensional object using the support material is also disclosed.
  • Three-dimensional (3D) printing is a type of additive manufacturing where the shapes of printed objects are modeled incrementally, layer by layer.
  • 3D printing is a process of making a 3D solid object from a digital model, where successive layers of material are laid down (i.e., by a 3D printer) in different shapes. After one layer is printed, the next layer is placed on top of it.
  • fused filament fabrication process also known as fused deposit modeling (FDM).
  • FFF fused filament fabrication process
  • FDM fused deposit modeling
  • a three-dimensional object is produced by extruding a thermoplastic material through a nozzle to form layers as the thermoplastic material hardens after extrusion.
  • a plastic filament is unwound from a coil and supplies thermoplastic material to the extrusion nozzle which con be turned on or off to control the flow.
  • the nozzle is heated to heat the thermoplastic material past its melting and/or glass transition temperature and is then deposited by the extrusion head on a base to form a three-dimensional object in a layer- wise fashion.
  • the thermoplastic material is typically selected, and its temperature is controlled so that it solidifies substantially immediately upon extrusion or dispensing onto the base, with the buildup of multiple layers to form the desired three-dimensional object.
  • the thermoplastic material is commonly known as a build material or a modeling material.
  • the thermoplastic materials are thermoplastic polymers such as polyethylene, polypropylene, acrylonitrile-butadiene-styrene (ABS) copolymers, polycarbonates, polyamides, and polylactic acids.
  • ABS acrylonitrile-butadiene-styrene
  • PVA polyvinyl alcohol
  • ABS polyvinyl alcohol
  • PVA and ABS can be printed simultaneously. After the 3D printing has been completed, the printed object can be submerged in water. The PVA is dissolved in warm water and leaves the ABS portion of the printed article intact.
  • PVA is quite difficult to print and does not sufficiently adhere to ABS.
  • PVA is highly sensitive to moisture and dissolved only in warm water.
  • Other known supporting materials cannot be used in FFF unless a substantial amount of additives such as plasticizers is used.
  • One aspect of the present disclosure provides a support material for three-dimensional printing comprising a blend of at least one cellulose ether and at least one vinyl pyrrolidone polymer.
  • Another aspect of the present disclosure provides a support material for three- dimensional printing comprising a blend of at least two cellulose ethers.
  • the cellulose ether is selected from the group consisting of hydroxypropyl cellulose, hydroxypropyl methyl cellulose, hydroxyethyl methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, carboxymethyl hydroxyethyl cellulose and combinations thereof. In one embodiment, the cellulose ether is hydroxypropyl cellulose or ethyl cellulose.
  • the cellulose ether is hydroxypropyl cellulose having a weight average molecular weight in the range of from 2,000 to about 2,000,000 Daltons. In another embodiment, the weight average molecular weight of the hydroxypropyl cellulose is from about 3,000 to about 1 ,000,000 Daltons. In another embodiment, the weight average molecular weight of the hydroxypropyl cellulose is from about 5,000 to about 500,000 Daltons. In one embodiment, the molar substitution of the hydroxypropyl cellulose is from 2.0 to 5.0. In another embodiment, the molar substitution of the hydroxypropyl cellulose is from 2.5 to 4.6. In another embodiment, the molar substitution of the hydroxypropyl cellulose is from 3.0 to
  • the cellulose ether is ethyl cellulose having ethoxy contents in the range of from 35 wt.% to 60 wt.%.
  • the vinyl pyrrolidone polymer is selected from the group consisting of a polyvinyl pynolidone (PVP), an alkylated polyvinyl pyrrolidone, a vinyl pyrroli done/vinyl acetate (VP/VA) copolymer, a vinyl pyrrolidone/dimethylaminoethylmethacrylate (VP/DMAEMA) copolymer, a vinyl pyrrolidone/dimethylaminopropylmethacrylamide (VP/DMAPA) copolymer, a vinyl pyrrolidone/methacrylamidopropyl trimethylammonium chloride copolymer, a vinyl pyrrolidone/dimethylaminopropylmethacrylamide/methacrylamidopropyl
  • PVP polyvinyl pynolidone
  • VP/VA vinyl pyrroli done/vinyl acetate
  • VP/DMAEMA vinyl
  • the weight average molecular weight of the vinyl pyrrolidone polymer is from about 1 ,000 to about 3,000,000 Daltons. In another embodiment, the weight average molecular weight of the vinyl pyrrolidone polymer is from about 2,000 to about 1,000,000 Daltons. In another embodiment, the weight average molecular weight of the vinyl pyrrolidone polymer is from about 3,000 to about 200,000 Daltons. [0012] In one embodiment of the present disclosure, the ratio of the cellulose ether to the vinyl pynolidone polymer is from about 95:5 to about 5:95 by weight. In another embodiment, the ratio is from about 95:5 to about 25:75 by weight. In still another embodiment, the ratio is from about 90:10 to about 50:50 by weight.
  • the support material is present in a solid state of powder or granulate.
  • Another aspect of the present disclosure provides a shaped material comprising the support material of the present disclosure.
  • the shaped material has a shape of a pellet, a rod, or a filament.
  • the build material is selected from the group consisting of acrylonitrile butadiene styrene (ABS) copolymers, polylactic acid (PLA), polyamides, polyethylene, polypropylene, polycarbonates, polyoxymelhylene (POM), ethylene vinyl acetate copolymers, polyphenylene ether, acrylonitrile styrene acrylate (ASA) copolymers, polyethylene terephthalate (PET), PETG (PET with a glycol modification), high impact polystyrene (HIPS), polyether ether ketone (PEEK), thermoplastic polyurethane, polyetherimide, and combinations thereof.
  • ABS acrylonitrile butadiene styrene
  • PLA polylactic acid
  • POM polyoxymelhylene
  • ASA acrylonitrile styrene acrylate
  • PET polyethylene terephthalate
  • PETG PET with a glycol modification
  • HIPS high impact polysty
  • the support material of the present disclosure is used for supporting at least one layer of a build material.
  • the build material is selected from the group consisting of acrylonitrile butadiene styrene (ABS) copolymers, polylactic acid (PLA), polyamides, polyethylene, polypropylene, polycarbonates, polyoxymelhylene (POM), ethylene vinyl acetate copolymers, polyphenylene ether, acrylonitrile styrene acrylate (ASA) copolymers, polyethylene terephthalate (PET), PETG (PET with a glycol modification), high impact polystyrene (HIPS), polyether ether ketone (PEEK), thermoplastic polyurethane, polyetherimide, and combinations thereof.
  • ABS acrylonitrile butadiene styrene
  • PLA polylactic acid
  • POM polyoxymelhylene
  • ASA acrylonitrile styrene acrylate
  • PET polyethylene tere
  • the three-dimensional printing comprises a fused deposition modeling.
  • Another aspect of the present disclosure provides a process for producing a three- dimensional object wherein the process comprising the steps of:
  • the build material is selected from the group consisting of acrylonitrile butadiene styrene (ABS) copolymers, polylactic acid (PLA), polyamides, polyethylene, polypropylene, polycarbonates, polyoxymethylene (POM), ethylene vinyl acetate copolymers, polyphenylene ether, acrylonitrile styrene acrylate (ASA) copolymers, polyethylene terephthalate (PET), PETG (PET with a glycol modification), high impact polystyrene (HIPS), polyether ether ketone (PEEK), thermoplastic polyurethane, polyetherimide, and combinations thereof.
  • ABS acrylonitrile butadiene styrene
  • PLA polylactic acid
  • POM polyoxymethylene
  • ASA acrylonitrile styrene acrylate
  • PET polyethylene terephthalate
  • PETG PET with a glycol modification
  • HIPS high impact polystyrene
  • the liquid medium comprises water, an aqueous solution and a solvent.
  • the liquid medium is the aqueous solution having a pH of about 5.0 to about 9.0.
  • the designated value may vary by plus or minus twelve percent, or eleven percent, or ten percent, or nine percent, or eight percent, or seven percent, or six percent, or five percent, or four percent, or three percent, or two percent, or one percent.
  • the use of the term“at least one” will be understood to include one as well as any quantity more than one, including but not limited to, 1, 2, 3, 4, 5, 10, 15, 20, 30, 40, 50, 100, etc.
  • the term“at least one” or“at least two” may extend up to 100 or 1000 or more depending on the term to which it is attached.
  • the quantities of 100/1 (XX) are not to be considered limiting as lower or higher limits may also produce satisfactory results.
  • the words“comprising” (and any form of comprising, such as “comprise” and“comprises”),“having” (and any form of having, such as“have” and“has”), “including” (and any form of including, such as“includes” and“include”) or“containing” (and any form of containing, such as“contains” and“contain”) are inclusive or open-ended and do not exclude additional, unrecited elements or method steps.
  • the terms“or combinations thereof’ and“and/or combinations thereof’ as used herein refer to all permutations and combinations of the listed items preceding the term.
  • “A, B, C, or combinations thereof’ is intended to include at least one of: A, B, C, AB, AC, BC, or ABC and, if order is important in a particular context, also BA, CA, CB, CBA, BCA, ACB, BAC, or CAB.
  • expressly included are combinations that contain repeats of one or more items or terms, such as BB, AAA, AAB, BBC, AAABCCCC, CBBAAA, CABABB, and so forth.
  • BB BB
  • AAA AAA
  • AAB AAA
  • BBC AAABCCCCCC
  • CBBAAA CABABB
  • support material describes the material which forms a support structure for overhangs or narrow cavities and the like of the three- dimensional object made from the modeling material during the FFF process.
  • the present disclosure is directed to a support material for three-dimensional printing.
  • the support materials can be a blend comprising at least two cellulose ethers.
  • the support materials can be a blend comprising at least one cellulose ether and at least one vinyl pyrrolidone polymer.
  • the cellulose ether can include, but are not limited to, hydroxypropyl cellulose, hydroxypropyl methyl cellulose, carboxymethyl cellulose, hydroxyethyl methyl cellulose, methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, carboxymethyl hydroxyethyl cellulose and their combinations.
  • the cellulose ether can have weight average molecular weights in a range of from about 2,000 to about 2,500,000 Daltons, or from about 3,000 to about 2,000,000 Daltons, or from about 4,000 to about 1000,000 Daltons, or from about 5,000 to about 500,000 Daltons.
  • the cellulose ether can be hydroxypropyl cellulose.
  • a molar substitution of the hydroxypropyl cellulose can be from about 2.0 to about 5.0, or from about 2.5 to about 4.6, or from about 3.0 to about 4.4.
  • the cellulose ether can be ethyl cellulose (EC).
  • EC ethyl cellulose
  • the ethoxy contents of the ethyl cellulose can be from about 35% to about 60%, or from about 40% to about 55%, or from about 45% to about 55%.
  • the vinyl pyrrolidone polymer used in the present disclosure can be a homopolymer, a copolymer, a terpolymer and/or a tetrapolymer of vinyl pyrrolidone.
  • the vinyl pyrrolidone polymer can include, but are not limited to, a polyvinyl pyrrolidone (PVP), an alkylated polyvinyl pyrrolidone, a vinyl pyrrolidone/vinyl acetate (VP/VA) copolymer, a vinyl pyrrolidone/dimethylaminoethylmethacrylate (VP/DMAEMA) copolymer, a vinyl pyrrolidone/dimethylaminopropylmethacrylamide (VP/DMAPA) copolymer, a vinyl pyrrolidone/methacrylamidopropyl trimethylammonium chloride copolymer, a vinyl pyrrolidone/di
  • trimethylammonium chloride terpolymer a vinyl pyrrolidone/aciylic acid/lauryl methacrylate terpolymer, a vinyl pyrrolidone/acrylic acid copolymer, a vinyl pyrrolidone/vinyl caprolactam copolymer, a vinyl pyrrolidone/vinyl caprolactam/ dimethylaminoethylmethacrylate terpolymer, a vinyl pyrrolidone/vinyl caprolactam/ dimethylaminopropylmethacrylamide terpolymer.
  • the vinyl pyrrolidone polymer is alkylated polyvinyl pyrrolidone.
  • the alkylated polyvinyl pyrrolidone can be prepared by homopolymerization of N- vinylpyrrolidone or a lower alkyl substituted N-vinylpyrrolidone and subsequent alkylation with an alpha-olefin of at least 2 carbon atoms, or from about 4 to about 30 carbon atoms. Also, these polymers can be prepared by copolymerization of N-vinylpyrrolidone with an alpha- olefin of at least 2 carbon atoms or from about 4 to about 30 carbon atoms.
  • the vinyl pyrrolidone polymers can have weight average molecular weights in a range of from about 1,000 to about 3,000,000 Daltons, or from about 2,000 to about
  • a ratio of the cellulose ether to the vinyl pyrrolidone polymer can be from about 95:5 to about 5:95 by weight, or from about 95:5 to about 25:75 by weight, or from about 90: 10 to about 50:50 by weight.
  • a ratio of the two cellulose ethers can be from about 99: 1 to about 1 :99 by weight, or from about 95:5 to about 25:75 by weight, or from about 92.5:7.5 to about 50:50 by weight.
  • the support material may further comprise additives, different from the above- mentioned blend, such as rheological modifiers, stabilizers, lubricants, fillers, plasticizers, pigments and/or impact modifiers.
  • additives different from the above- mentioned blend
  • an advantage of the present disclosure is that the presence of such additives different from the above-mentioned blend is optional.
  • Another advantage of the support material in the present disclosure is that it can be dissolved at room temperature or even low temperatures. Thus, no heat is needed for the dissolution of the support material.
  • Non-limiting examples of the fillers can include carbohydrates, sugars, sugar alcohols, proteins, inorganic salts/ceramics, graphene, graphite, carbon nanolube/fibers, glass fibers, metals and alloys.
  • Inorganic salts/ceramics can include, but are not limited to, oxides, carbides, nitrides, silicates, aluminum silicates, titanates, clay, mica, calcium carbonate, aluminum magnesium silicates, phosphates, chlorides, nitrates, borates, borides, sulfites, sulfides and sulfates.
  • Metals and alloys can include, but are not limited to, iron, steel, nickel, cobalt, aluminum, titanium, copper, silver, gold and their alloys.
  • Examples of the lubricants can include, but are not limited to, polyethylene oxide homopolymers, copolymers and terpolymers; glycols; or oil lubricants, such as light mineral oil, com oil; high molecular weight polybutenes; polyol esters; a blend of light mineral oil and wax emulsion; a blend of paraffin wax in com oil; hydrocarbon waxes; metal fatty acid salts such as magnesium stearate and calcium stearate: polytetrafluoroethylene; graphite and combinations thereof.
  • the amounts of the lubricants can be from about 0.1 to about 20 percent, or from about 0.3 to about 10 percent, based on the total weight of the blend.
  • Stabilizers are mainly antioxidants and UV absorbers, including ascorbic acid, N, N'- di-2-butyl- 1 ,4-phenylenediamine, butylated hydroxytoluene, di-iert-butylphenol, dimethyl-6- tert-butylphenol, oxanilides, benzophe nones, benzotriazoles and hydroxyphenyluiazines.
  • Plasticizer includes phosphates; phlhalates such as dibutyl phlhalate, dicyclohexyl phthalate, benzyl phthalate; and diphenyl phthalate; adipates; sebacates such as dibutyl sebacate; maleates; citrates such as triethyl citrate; polyethylene glycols; benzoates; organophosphaies such as cresyl diphenyl phosphate; sulfonamides; stearates such as butyl stearate; sorbitol; sobitan monolaurates; soibitan monopalmitates; sorbitan monostearates; sorbitan monooleates; glycerides; esters of higher fatty acids and amides; glycol esters of coconut oil fatty acids; acetylated monoglyceride; glycerine; castor oil; butyl phthalyl butyl glycolate; buty
  • Pigments includes inorganic pigments and organic pigments.
  • Inorganic pigments include carbon, clay or metal pigments based on cadmium, chromium, cobalt, copper, iron, lead, manganese, mercury, titanium, zinc or aluminum.
  • Common organic pigments include azo pigments, lake pigments, phthalocyanine pigments and quinacridone pigments. Some examples are pigment yellow 3, 6, 14, 17, 65; pigment red 12, 122, 4, 13; pigment blue 1, pigment violet 3, pigment orange 5 etc.
  • Uniform mixing of the blends with one or more optional additives e.g., selected from fillers, lubricants, stabilizers and antioxidants to produce the support material can be accomplished by, for example, a known conventional kneading process.
  • the blends used as support materials in the present disclosure can be provided in a shaped material in a form of a filament, pellet or rod.
  • the support materials of the present disclosure can be removed by immersing, spraying with or contacting with a liquid medium including water, an aqueous solution and/or a solvent depending on the specific blend.
  • a liquid medium including water, an aqueous solution and/or a solvent depending on the specific blend.
  • the temperature of the liquid medium can be normally varied in a range of about 0 to about 100 °C, or about 2 to about 40 °C, or about 4 to about 36 °C.
  • the water can be any types of water including tap water, deioni/ed water and distilled water.
  • the term“solution” includes full solutions in which the solutes are fully dissolved in water or aqueous solvent, and partial solutions in which the solutes are at least partially dissolved in water or the aqueous solvent.
  • Suitable solutes can be water-soluble inorganic salts, for example, an alkali metal salt and an alkaline earth metal salt.
  • the alkali metal salt is for example an alkali metal halide selected from sodium chloride, potassium chloride, sodium iodide and sodium bromide.
  • the alkaline earth metal salt is for example an alkaline earth metal halide selected from calcium chloride and magnesium chloride.
  • the aqueous solution can have a pH value in a range of about 6 to about 9, or about 6 to about 8.
  • the aqueous solutions may also be agitated and/or subjected to ultrasonic frequencies.
  • the solvents can be water-miscible organic solvents or non-polar organic solvents.
  • examples can include, but are not limited to, low molecular weight alcohols such as ethanol, methanol, isopropanol, propanol and butanol; ketones such as acetone, methyl ethyl ketone, methyl propyl ketone and isopropyl methyl ketone; alkyl acetates such as methyl acetate and ethyl acetate; pyrrolidines such as 2-pyrolidone, N-methyl-2- pyrrolidone, N-ethyl-2-pym>lidone and N-hydroxyethyi-2-pynolidone; hexane; heptane; cyclohexane; kerosene; mineral spirits; tetrahydrofuran; toluene; xylene; mineral oil; linseed oil;
  • the solvent can be limonene.
  • the blend used as a support material according to the present disclosure shows significantly shorter times for solubilization, better adhesion to a build material and better printability in a 3D printer compared to support materials known in the state of the art.
  • the blend can be easily removed from a three-dimensional object printed from the 3D printer.
  • elevated temperatures are not needed to dissolve the support material in a liquid medium.
  • the build material used in the present disclosure can be any thermoplastic materials comprising a thermoplastic polymer. Accordingly, any thermoplastic material capable of being extruded may be used. Suitable build materials can include, but are not limited to, polyolefins like polyethylene or polypropylene, acrylonitrile-butadiene-styrene (ABS) copolymers, polycarbonates, polyamides, polylactic acids and blends of the aforementioned polymers.
  • ABS acrylonitrile-butadiene-styrene
  • the build materials used in the present disclosure can also include, but are not limited to, acrylonitrile butadiene styrene (ABS) copolymers, polyoxymethylene, polylactic acid (PLA), ethylene vinyl acetate copolymers, polyphenylene ether, ethylene-acrylic acid copolymer, polyether block amide, polybutylene terephthalate, polyethylene terephthalate (PET), polycyclohexylenedimethylene terephthate, polyphenylene sulfide, polyphlhalamide (PPA), polymethylmethacrylate, polysulfones, polyphenylsulfones, polyacrylonitrile, polystyrene, polyolefins including polyethylene and polypropylene, polyvinyl butyral, polyvinyl chlorides, polyurethanes, polyamides, polycarbonates, polyoxymethylene (POM), ethylene vinyl acetate copolymers, polyphenyrene (
  • The“layer-based additive technique” for the purpose of the present disclosure is a technique, wherein a first layer of material is deposited on a base in a build chamber to form a first layer of material, followed by the deposition of a second layer of material on the first layer of material, followed by the deposition of a third layer of material and so on.
  • the number of layers deposited by the layer-base additive technique depends on the size of the three- dimensional object and the support structure respectively. Moreover, the number of layers depends on the thickness of the layers deposited.
  • An FFF-process fused filament fabrication process in the present disclosure is a process in which at least one build material and at least one support material are each initially present in a solid state and thereafter melted and printed to form a three-dimensional object comprising the modeling material, which is supported by the support material. Subsequently the support material is removed by dissolving to obtain the three-dimensional object itself.
  • the present disclosure also relates to a process for producing a three-dimensional object which comprises: (i) depositing a support material comprising the above-described blend into a build chamber with a layer-based additive technique to form a support structure, optionally on a substrate; (ii) depositing a build material as described above into the build chamber with the layer-based additive technique to form the three-dimensional object comprising at least one region supported by the support structure; and (iii) removing the support structure from the three-dimensional object with a liquid medium.
  • Suitable substrates on which the three-dimensional object is formed are known in the art, such as plates or sheets made of glass, metal or synthetic materials.
  • the process can be carried out according to fused deposition modeling (FDM).
  • FDM fused deposition modeling
  • At least one build material and at least on support material are each initially present in a solid state and thereafter melted in nozzles and printed to form a three-dimensional object comprising the build material, which is supported by the support material.
  • the support material is removed by dissolving in a liquid medium to obtain the three-dimensional object itself.
  • the build material and the support material can be heated to the same or different temperatures to bring them into a molten or softened shape.
  • Dissolution of the support material can be carried in a way known in the art.
  • the three-dimensional object comprising the build material and the support material can be brought in contact with the liquid medium.
  • the three-dimensional object comprising the build material and the support material therefore can simply be placed in a bath comprising the liquid medium.
  • Experimental filaments with diameter oG 1 ,7-2mm were made on a Leistritz-18 mm twin screw co-rotating hot melt extruder (HME) equipped with a 2 mm die (commercially available from Leistritz Extrusion Technologies Corp., Germany).
  • HME hot melt extruder
  • the HME process parameters are listed in Table 1.
  • the experimental filaments were made using HPC, HPC and additives, blends of HPC and EC, and blends of HPC and VP polymer.
  • the experimental filaments of VP polymers alone were very brittle and easily broken. Such filaments could not be used as support materials for printing.
  • the filament samples were cut to about 2 * in length, then were dried in an 80°C oven for 2 hours, before being allowed to sit on a bench in air at about 20 to 25 °C for about one week to absorb moisture. Then the filament samples were weighed and put back into the 80°C oven. The samples were then weighed at 4 and 18 days. The data is listed in Table 2. The weight ratio is Component 1 to Component 2.
  • the filaments were cut into about 0.6 g of such filaments were added into a beaker containing 200 g tap water at 20-25 °C. The filaments were dissolved without stirring. The dissolution times were recorded and shown in Table 2. Table 2. Moisture and Dissolution Time Measurement
  • the adhesion test was performed on a heated steel plate.
  • the steel plate was wrapped with a Teflon-coated steel foil.
  • the support filaments were cut into about G length segment, then placed on the heated Teflon-coated foil.
  • ABS filaments of G were put on the support filaments in a cross direction.
  • the temperature of the heated plate was increased to about 185°C.
  • a tweezer was used to manually press the ABS filament to the softened support filaments.
  • the filaments were then cooled down to 20-25 °C.
  • the adhesion strengths of Samples 1-2 and 4-7 were the same.
  • the filament of Sample 3 had stronger adhesion than the filaments of Samples 1-2 and 4-7.
  • the support materials having the blend of hydroxypropyl cellulose and vinyl pyrrolidone polymers or the blend of hydroxypropyl cellulose and ethyl cellulose have the same or better adhesion than hydroxypropyl cellulose alone.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Mechanical Engineering (AREA)
  • Optics & Photonics (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

La présente invention concerne de manière générale un matériau de support pour impression en trois dimensions comprenant un mélange d'au moins deux éthers de cellulose ou un mélange d'au moins un éther de cellulose et d'au moins un polymère de vinylpyrrolidone. De plus, la présente invention concerne un matériau façonné et un objet imprimé en trois dimensions comprenant le matériau de support. L'invention concerne en outre un procédé de production d'un objet tridimensionnel à l'aide du matériau de support.
PCT/US2019/054961 2018-10-05 2019-10-07 Matériaux de support pour impression tridimensionnelle Ceased WO2020073040A1 (fr)

Priority Applications (1)

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US17/282,949 US20210387422A1 (en) 2018-10-05 2019-10-07 Support materials for three-dimensional printing

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US201862742198P 2018-10-05 2018-10-05
US62/742,198 2018-10-05

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US11524449B2 (en) * 2018-11-27 2022-12-13 3D Systems, Inc. Method for preparing a surface for extrusion deposition modeling
FR3131244B1 (fr) * 2021-12-23 2024-04-19 Thales Sa Procede de fabrication d une piece multi-materiaux polymere et metallique et/ou dielectrique.
WO2023125367A1 (fr) * 2021-12-29 2023-07-06 苏州聚复科技股份有限公司 Fil d'impression 3d et son procédé de préparation, procédé d'impression 3d et appareil d'impression

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US20140162033A1 (en) * 2010-10-27 2014-06-12 Eugene Giller Process and Apparatus for Fabrication of Three-Dimensional Objects
US20160194492A1 (en) * 2013-07-26 2016-07-07 Hewlett-Packard Development Company, L.P. Composite support material for three-dimensional printing
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